Permanganate-coated ozone for groundwater and soil treatment with in-situ oxidation

ABSTRACT

Permanganate is delivered by a device that allows delivery of the permanganate and an air-ozone mixture to a soil formation. The permanganate can be delivered as a coating over microbubbles including the air/ozone gas stream.

This application is a continuation-in-part, claims the benefit of, andincorporates by reference in its entirety, U.S. patent application Ser.No. 10/895,015; filed Jul. 20, 2004 and entitled “Superoxidant Poiserfor Groundwater and Soil Treatment with In-Situ Oxidation-Reduction andAcidity-Basicity Adjustment.”

BACKGROUND

This invention relates generally to water remediation systems andtechniques.

There is a well-recognized need for removal of subsurface contaminantsthat exist in aquifers and surrounding soils. Such contaminants caninclude various man-made volatile hydrocarbons including chlorinatedhydrocarbons, e.g., volatile organic compounds such as chlorinatedolefins including trichloroethene (TCE), tetrachloroethene (PCE), cis1,2-dichloroethene, vinyl chloride and 1,4 Dioxane, mixed in withchloroethenes and so forth. Other compounds include aromatic orpolyaromatic ring compounds such as benzene, toluene, methylbenzene,xylenes, naphthalene, and propellants or explosives such asnitroanilines, trinitrotoluene, and so forth. The groups of compoundsare characterized by aromatic ring structures also include alkylsubstituted aromatic hydrocarbons.

Chemical oxidants such as permanganate, oxygen, ozone, hydrogen peroxideare used for treatment of certain contaminants. Permanganate has anadvantage over certain of these chemical oxidants because of its longhalf-life which is measured in months. Current practices of in-situoxidation, with a permanganate involves directly injecting permanganateinto unsaturated or groundwater saturated soils to induce chemicaloxidation reactions with contaminants.

SUMMARY

Application of permanganate using current practices has disadvantages.For example, permanganate is poorly reactive with 1,4 dioxane andbenzene, limiting its use with certain mixtures of these compounds withchloroethenes. When applied as a liquid wash, permanganate producescarbon dioxide gas (CO₂) and manganese dioxide (MNO₂), a precipitate,which slows down the effectiveness of the permanganate over time.

Typically, when released into saturated soils at the top of an aquifer,the permanganate tends to displace water because of its density andmoves downwards, often irregularly according to conditions of the soil,e.g., if the soil is partially laid down in layers the permanganate canmove in fluvial channels, and so forth.

Permanganates may be involved in secondary reactions with soil orbedrock matrix. Such secondary reactions can occur for example withpermanganates such as potassium or sodium permanganates. That is, thepermanganates tend to react excessively with the soil minerals,lessening the permanganates efficiency as an oxidant. Examples ofsecondary reactions include those involving metallic or nonmetallic cations such as iron (Fe⁺² or Fe⁺³), manganese (Mn⁺² or Mn⁺⁴), calcium(Ca⁺²), copper (Cu⁺² and Cu⁺¹), chromium (Cr⁺³ and Cr⁺⁶), and so forth.These cations under oxidation can become involved in secondary reactionsminimizing the effectiveness of the added potassium permanganate orsodium permanganate and causing undesirable by-products.

Some or all of these disadvantages can be overcome by using permanganateor a precursor, e.g., potassium manganate with ozone, such as in acoating on microbubbles entrapping an air/ozone gas mixture. Generally,the microbubbles are of the order of 0.1 microns to 200 microns.

According to an aspect of the present invention, a method includesintroducing an air stream including ozone delivered with a permanganateto decompose contaminants, with the permanganate to ozone being in amolar ratio of 1-20 to 1.

The following are embodiments within the scope of the claims. Thepermanganate is delivered as a coating over microbubbles including theair/ozone gas stream. Introducing includes introducing air and ozoneinto the soil through a microporous diffuser. Introducing includesintroducing air and ozone as the gas and the permanganate as a liquidinto a microporous diffuser. The microporous diffuser includes promotersor nutrients such as catalyst agents including iron containing compoundssuch as iron silicates or palladium containing compounds such aspaladized carbon and platinum that contact microbubbles that emanatefrom the microporous diffusers. The microporous diffusers have a poresize in the range of about 0.1 to 200 microns. The air/ozone has up to10% ozone by volume as a gas entrapped in microbubbles. The permanganateis up to 40 percent liquid volume as a liquid that coats themicrobubbles. Introducing includes introducing air and ozone as a gasmixture entrapped in microbubbles and sodium permanganate as a liquidcoating over the microbubbles. The permanganate is selected from thegroup consisting of sodium permanganate and potassium permanganate andprecursor, potassium manganate.

According to an additional aspect of the present invention, a method oftreating contaminants in a formation includes introducing ahydro-peroxide into the formation and introducing an air/ozone gasstream delivered with a permanganate into the formation to decompose thecontaminants.

The permanganate is delivered as a surface layer over microbubblesincluding the air/ozone gas stream. The hydro-peroxide is delivered as asurface layer over microbubbles including an air/ozone gas stream. Thepermanganate is delivered as a surface layer over microbubbles includingthe air/ozone gas stream, and the hydro-peroxide is delivered as asurface layer over different microbubbles including an air/ozone gasstream. Introducing peroxide includes introducing air and ozone as a gasand the hydro-peroxide as a liquid into a microporous diffuser.Introducing permanganate includes introducing air and ozone as a gas andthe permanganate as a liquid into a microporous diffuser. The methodincludes waiting for a period of time after introducing thehydro-peroxide before introducing the permanganate. The method includeswaiting for a period of time after introducing the hydro-peroxide beforeintroducing the permanganate to allow the hydro-peroxide to decomposebefore introducing the permanganate. The microporous diffusers have apore size in the range of about 0.1 to 200 microns. Introducing includesintroducing air and ozone as a gas entrapped in microbubbles and sodiumpermanganate as a liquid coating over the microbubbles. The air/ozone isozone up to 10% volume as a gas entrapped in microbubbles and potassiumpermanganate is in a ratio of 1-20 to 1 of permanganate to ozone.

According to an additional aspect of the invention, an apparatusincludes a source of permanganate, a diffuser that allows delivery ofthe permanganate and air ozone to a soil formation and a mechanism todeliver the permanganate and air/ozone to the diffuser. The apparatusalso includes a controller to control delivery of the permanganate andthe air/ozone to the mechanism.

One or more of the following advantages may be provided by one or moreaspects of the invention.

The combination of ozone and permanganate allows fast-acting ozone toreact with 1,4 Dioxane, Benzene, and its derivatives, expanding theoxidative potential of the permanganate with other compounds.

Because permanganate is transported with microbubbles, it is activelydispersed rather than relying on density alone to distribute thepermanganate. Thus, the microbubble transport mechanism provides betterdiffusion and distribution of permanganate laterally, since buoyancywill push the coating laterally and upwards through the formation,reducing the tendency to form dense vertical chimneys with only lateralspreading in highly permeable layers by downwards density spreading. Thebuoyancy of the microbubbles can be controlled by adjusting density ofthe permanganate and thickness on the microbubble. The density of thepermanganate coating on the microbubbles allows for the adjustment ofthe buoyancy of the coated micro or nano sized bubbles, since with athick enough coating neutral buoyancy can be reached.

The microbubbles allow for a more effective distribution of thepermanganate in both laterally and vertically dimensions thandensity-driven dispersion of prior techniques. With use of bubblesurging or pulsing the bubbles can remove CO₂ and loosen up crustformations, improving longer-term reactivity of permanganate. Thecoating of sodium or potassium permanganate on the microbubbles drawingcontaminates such as highly volatile or volatile organic compounds topermanganate coating according to Henry's Constant, thus reducing sidereactions of the sodium or potassium permanganates with mineral surfacesin the soil substrate. Through the use of Henry'is partitioning fromliquid to gas, volatile organic ethenes are “extracted” or drawn intothe coating improving reaction efficiency.

The combination of the ozone-air in the microbubbles and thepermanganate increases the oxidation potential of the permanganate,allowing treatment of 1,4 Dioxane, mixed in with chloroethenes. Examplesof permanganates include sodium and potassium permanganates.

The details of one or more embodiments of the invention are set forth inthe accompanying drawings and the description below. Other features,objects, and advantages of the invention will be apparent from thedescription and drawings, and from the claims.

DESCRIPTION OF DRAWINGS

FIG. 1 is a diagram depicting an apparatus for recirculation wellsystem.

FIG. 2 is a diagram depicting an apparatus for a dual point well system.

FIG. 3 is a flow chart of another treatment flow.

FIGS. 4-6 are diagrams depicting various treatment configurations.

DETAILED DESCRIPTION

Referring to FIG. 1, an example for a treatment system 10 to treatcontaminants in a subsurface aquifer 12 includes a sparging apparatus 14that is disposed through a soil formation 16. In this arrangement, thesparging apparatus 14 is disposed through a soil formation 16 e.g., avadose zone 16 a and an underlying aquifer 12. The sparging apparatus 14includes a casing 18 positioned through a borehole disposed through thesoil formation 16. The casing 18 has an inlet screen 18 a disposed on anupper portion thereof and an outlet screen 18 b disposed on a bottomportion thereof. Disposed through the casing 18 is a first microporousdiffuser 50 a. Alternatively, a slotted well-screen could be used. Themicroporous diffuser 50 a is a laminate microporous diffuser. A secondmicroporous diffuser 50 b is disposed in a borehole that is below theborehole containing the casing 18, and is surrounded by a sand pack andisolated by Bentonite or a grout layer from the borehole that has thefirst microporous diffuser 50 a. Also disposed in the casing is a packer17 that isolates the upper screen 18 a from the lower screen 18 b andappropriate piping to connect sources of decontamination agents to themicroporous diffusers 50 a, 50 b. When fluid is injected through themicroporous diffusers 50 a, 50 b the packer 17, screens 18 a, 18 b and awater pump 19 enable a re-circulation water pattern 13 to be produced inthe soil formation.

As shown in FIG. 2, other arrangements are possible. For instance, thearrangement could use two microporous diffusers packed in a sand pack,e.g., a 60 mesh sand pack, which are separated by a Bentonite layer.This arrangement is an example of a non-recirculation arrangement thus,obviating the need for the packer for instance. Still other arrangementsare possible.

The arrangement 10 (or 10′) also includes apparatus 25 including agaseous decontaminate oxidizer apparatus 30 and a liquid oxidizer supplyapparatus 40 that supplies potassium or sodium permanganate or apermanganate precursor such as potassium manganate. Generally, the gassources on the oxidative side can be air, oxygen, and ozone. Some of thesources can be supplied via the ambient air, e.g., an oxygen generatorand an ozone generator can be used to supply oxygen and ozone from air.The liquid supply apparatus feeds a liquid mixture the microporousdiffusers 50 a, 50 b. The liquid source is a permanganate (potassium orsodium) solution for example. The system feeds the microporous diffusers50 a, 50 b with the gas stream, typically air and ozone through acentral portion of the microporous diffuser producing microbubbles thatexanimate from the central portion of the microporous diffuser wherethey come in contact with the permanganate solution, producingmicrobubbles with a permanganate coating on the bubbles.

Typically, the permanganate solution is maintained at a molar ratio ofabout 1-3 to 1 (permanganate to ozone), more specifically, 1 to 1 forefficient reactivity. This is equivalent to about 3 grams ofpermanganate to 1 gram of ozone (2.47 gms. MnO4 to 1 gm O3).

Under field conditions, permanganate, like peroxide, would tend to reactmore frequently with soil minerals, requiring a ratio of 1-20 to 1 or 1to 20 times (more specifically 4-20 to 1) the ozone mass weight tocompensate for soil natural oxidant demand (NOD) loss. The air/ozonemixture can have ozone up to about 10% volume as a gas entrapped inmicrobubbles, and potassium permanganate as a liquid coating over themicrobubbles.

Several advantages are provided by coated microbubbles entrapping anair-ozone gas, with the sodium or potassium permanganate. Becausepermanganate is transported with microbubbles, it is actively dispersedrather than relying on density alone to distribute the permanganate.Thus, the microbubble transport mechanism provides better diffusion anddistribution of permanganate laterally, since buoyancy will push thecoating laterally and upwards through the formation, reducing thetendency to form dense vertical chimneys with only lateral spreading inhighly permeable layers by downwards density spreading.

In addition, the density of the permanganate coating on the microbubblesallows for the adjustment of the buoyancy of the coated micro or nanosized microbubbles, since with a thick enough coating neutral buoyancycan be reached.

The coating of sodium or potassium permanganate on the microbubblesdrawing contaminates such as highly volatile or volatile organiccompounds to permanganate coating according to Henry's Constant, andthus reducing side reactions of the sodium or potassium permanganateswith mineral surfaces in the soil substrate.

The combination of the ozone-air in the microbubbles and the sodium orpotassium permanganate increases the oxidation potential of thepermanganate, allowing treatment of 1,4 Dioxane, mixed in withchloroethenes for example. This is an especially commercially usefulexample because in states such as California the compound 1,4 Dioxanewas often added to containers holding chloroethenes to inhibit corrosionof the container. In California the 1,4 Dioxane the maximum permissiblecontaminant level (MCL) is set at 4 ppb, an even more stringent levelthan levels set for the chloroethenes.

Referring to FIG. 3, another treatment flow is shown. This treatmentinvolves the use of a peroxide treatment followed by permanganatetreatment with the permanganate coated microbubbles. A preferredtreatment with peroxide is disclosed in U.S. Pat. No. 6,436,285 entitled“Laminated Microporous Diffuser” and/or U.S. Pat. No. 6,582,611 entitled“Groundwater and Subsurface Remediation,” both of which are incorporatedherein by reference, although other treatments could be used such asdirect injection of a peroxide, such as hydrogen peroxide. The peroxidetreatments disclosed in the above applications involve the user ofperoxide coated microbubbles.

The treatment flow uses a hydro peroxide or hydrogen peroxide treatmente.g., such as a Perozone™ treatment (available from KerfootTechnologies, Inc. Mashpee Mass.) followed by treatment withpermanganate. Generally, the permanganate is injected after the hydrogenperoxide has had a sufficient time to decompose. Typically, the time forhydrogen peroxide to decompose is about 3 to 5 days. This can be sitespecific, based upon the carbonate content of the soil at the site.Groundwater sampling and peroxide analysis can be conducted to confirmthe absence of the peroxide.

This treatment flow would be useful for treating VOCs (chloroethenes)imbedded in other petroleum products (machine oil, diesel, TPH, etc.),which need digestion of the petroleum products to free the solvents forreaction. Other contaminants include pentachlorophenol (PCP) mixtures inmineral reactions where aromatic ring breaking with the higher oxidationpotential Perozone™ preceeds the permanaganate reactions with remainingchloroethene products are other possible procedures. These would involvea large number of aromatic and saturated ring compounds (chlorinatedPAHs, PCT, Cl Pesticides) whose ring structure needs to be opened forpermanganate attach on the chlorinated ethenes or ethanes.

Also supplied to the microporous diffusers can be promoters ornutrients, as well as catalyst agents 42 including iron containingcompounds such as iron silicates, ferrous iron, acetic acid, orpalladium containing compounds such as palladized carbon or othertransition metals in acid solution. In addition, other materials such asplatinum may alternatively be used. The promoters or nutrients can beintroduced with the permanganates.

The mixture of air/ozone affects substantial removal of contaminantssuch as various man-made volatile hydrocarbons including chlorinatedhydrocarbons, chlorinated olefins such as tetrachloroethylene,trichloroethylene, cis 1,2-dichloroethene and vinyl chloride and othercompounds e.g., aromatic ring compounds, propellants, explosives, and soforth that are found as contaminants.

The electronic and mechanical system to control the sparging apparatus10 or 10′ includes a gas pump and a liquid pump that are controlled viaa mechanical time sequencer, or computer based controller, as discussedbelow, either of which is programmed to deliver a selected mass of eachmaterial per unit time producing a mixture of predetermined oxidationpotential. The oxidation potential, the mass/time, pressure, and timesequence are set electronically. An oxygen generator feeds an ozonegenerator, allowing the ratio of ozone to oxygen to be set. The liquiddelivered is water and permanganates.

A less efficient technique to introduce liquid would include separatinggas introduction and liquid introduction in the substrate by usingsand-packing around a central gas introduction tube or by sequentiallyflooding the region with a liquid, like a permanganate, above or arounda single point and sending a fine bubble stream through a fine diffuserthrough the mixture. A secondary siphon-effect could be developed butthe uniformity of coating would not be as controlled as with thetechniques described above.

FIG. 4 shows a composite Laminar microporous diffuser arrangement (e.g.,a Laminar Spargepoint described in U.S. Pat. Nos. 6,436,285 and6,582,611 or obtainable from Kerfoot Technologies, Inc.) that producesan outside discharge of air/ozone bubbles having a coating ofpermanganate. To withstand higher ozone concentrations to maintain lowmolar ratios with permanganate, the Laminar Spargepoints® areconstructed of Kynar® and/or stainless steel. KYNAR® is a registeredtrademark of Elf Atochem North America, Inc. for a PolyvinylideneFluoride (PVDF) high molecular weight thermoplastic polymer withexcellent chemical inertness.

FIG. 5 shows a central water flow through an inverted cylindricalmicroporous diffuser, e.g., a Spargepoint® with an interior discharge(nozzle). The arrangement involves the discharge of water through thecenter of a microporous double cylinder with a non-permeable sheath. Thegas enters an outer zone between an outermost plastic or stainless steelbarrier and an inner microporous (0.5 to 200 micron) cylinder includingsupport material (rings or mesh) and flows towards the center. Liquid isdrawn into a microporous hydrophilic layer and coats a gas streampassing there through. The liquid and gas flows may be subject topulsing (±5 psi) of their flows at frequent intervals (e.g., 0.5 to 10times/sec) to provide an internal shear as the bubbles exit against theshearing force from the water or liquid velocity. With this arrangementnano to micro-size bubbles can be produced to flow in a water stream outfrom a well screen (either re-circulated vertically or provided fromsurface tank, flowing outwards or towards a laterally-located withdrawalwell).

FIG. 6 shows a vertical separation of permanganates with lower oxygenrelease. In the arrangement of FIG. 5, vertical separation occursbetween the cylinders of liquid introduction and gas introduction. Themicroporous gas generator is placed below the liquid generator so thatthe rising microbubbles pass through the liquid addition. Theintroduction cylinders can be segregated or supplied by a line passingthrough the center of the other. In either case, the bubbles rise whilethe denser upper liquid falls. A feed tubing arrangement can beconfigured with a line inside a line or by parallel tubes with anexternal sheath that is either wrapped or molded about the tubes.

The laminar microporous diffusers, U.S. Pat. Nos. 6,436,285 and6,582,611 or obtainable from Kerfoot Technologies, Inc. (gas/liquidSpargepoints®) or equivalents, deliver gas and liquid with thepermanganate to porous zones (vadose or saturated). The microporousdiffuser produces microbubbles that siphon a liquid coating, as bubblespulsed through capillary pores, yielding a water/coatingliquid/gas/coating liquid/water peristaltic transport throughmicroscopic capillary pores of the soil. The greater the hydrostaticpressure existing on the microporous diffuser, the higher the siphoningpressure produced. This indicates that with Boyle's Law of IncreasedPressure, the smaller the internal volume of the bubble causes aconcomitant enlargement of the microbubble due to capillary (meniscus)pressure to accommodate a higher surface area of the microbubble (ormicrocylinder) in the capillaries.

The cylindrical microporous diffuser, in which the gas is sent throughthe center of the microporous diffuser and through micropores across asandwiched hydrophobic microporous layer connected to the liquid supply,is the most efficient approach to produce the flow. The intense negativepressure developed during operation occurs without any pump powerprovided. A metering mechanism is desirable to maintain a constant flowof liquid, but if sufficient volume is not supplied, the liquid can besubjected to sufficient vacuum pressure to produce boiling (degassing)of the liquid. A vacuum relief check valve for each liquid source can beused to increase flow during these conditions.

The system uses air-ozone sparging where bubbles of air-ozone areinjected into treatment areas. When air is bubbled through ground waterin soil pores, dissolved VOCs transfer from the liquid to gas phase inaccordance with Henry's Law.

In accordance with Henry's Law, dissolved VOCs are driven into a gasphase and the gaseous ozone is driven into an aqueous phase. This willresult in various reactions occurring at the bubble-liquid interface,whether in the gas-film or liquid-film of the bubble. Whether theprimary decomposition reaction is occurring in the gaseous or liquidphase, oxygenates are driven by partitioning into the bubbleenvironment. The smaller the bubble, the greater the surface-to-volumeratio and the ability of the bubble to “strip” volatile organics, asdiscussed in (Kerfoot, et al., Tenth Annual Outdoor Actions ConferenceNational Groundwater Association Columbus OH pp 77-97 (1996).

The thin film theory of Henley and Seader (1981) Equilibrium StateSeparation Operations in Chemical Engineering Chapter 16, John White andSons, New York, N.Y., as summarized in Kerfoot (2002) Kerfoot, W. B.“Microbubble Ozone Sparging for Chlorinated Ethene SpillRemediation.”In: Innovative Strategies for the Remediation ofChlorinated Solvents and DNAPLS in the Subsurface American ChemicalSociety, Division of Environmental Chemistry, Washington, D.C.,describes the mass transfer of a reactant across a liquid and a gas filmbefore it contacts the other reactant.

The high surface to volume ratio of micron-sized bubbles enhances the insitu stripping capacity (partitioning from aqueous to gaseous phase) toallow effective extraction. Laminar Spargepoint®

The laminar Spargepoints® (or equivalent) are used to inject ozone andpermanganates into the ground. The laminar Spargepoints® are made of amicro-porous flouropolymer material, or microporous stainless steel. Asthe ozone and permanganates are pumped into the points, they are pushedout through the micro-pores, forming a permanganate encapsulated ozonebubble. The contents of the bubble react with the contamination in theground. Ozone may also be injected through microporous ceramic diffusersbelow liquid introduction by microporous or slotted screens.

Tubing

The tubing forms the connections between the C-Sparger® control paneland the hydrogen peroxide control panel to the laminar Spargepoints®.There are two types of tubing used. One is high density polyethylene orKynar, depending upon O₃ concentration for the lateral runs from thecontrol panels to the wells. The other is Teflon® in the control panelsand for the hydrogen peroxide flow from the wellhead to the laminarSpargepoint®. Other types of tubing that are resistant to ozone andhydrogen peroxide can be used.

Pulsing, Siphoning, and Residence Time for Maximizing Efficiency

Adjusting downwards the size of gas bubbles allows sufficiently slowrise time to allow adequate residence time for gas/aqueous reactions togo to completion. Pulsing allows the introduction of gas bubbles, coatedwith liquid or surrounded by liquid (if bubble diameter is equal to orgreater than capillary pore size) to be introduced, and reside in thevicinity of the compounds of concern for reaction and move upwardsduring the next pressure event. Rise time in saturated sands issubstantially reduced by reducing the diameter of the emittedmicrobubbles.

If a continuous gas flow were used instead of intermittent, a continuousgas channel would be produced (as envisioned by Clayton(1998))interfering with liquid coating of the gas bubbles, loweringefficiency of reaction by rapidly transporting unreacted ozone gas intothe vadose zone. Producing a continual gas flow (greater than 10 cfmthrough 0.010 inch slots, 1 meter long, 2 inches in diameter) canprovide vertical gas travel times of greater than 2 meters/minute. Incomparison, fine bubble production (0.5 to 50 micron size), can resultin vertical travel times of 0.01 to 0.1 meters/minute. By extending thehalf-life of ozone from 0.5 to 30 hours, the residence time for reactionin a 6-meter vertical contaminated zone increases from 60 to 600minutes, approaching the half-life of ozone.

Siphoning Effect

The movement of fine gas bubbles coated with liquid produces a lowerpressure as the bubbles are injected out into the formation throughLaminar Spargepoints®.

The higher the necessary gas pressure for operation against formationbackpressure, the greater the negative pressure siphoning in liquid.This phenomenon may reflect smaller size microbubbles with highersurface to volume ratios evolving from Boyle's Law of Pressure,requiring more liquid to cover the emitted gas volume. Surface tensionof the liquid would cause more liquid to be delivered.

A number of embodiments of the invention have been described.Nevertheless, it will be understood that various modifications may bemade without departing from the spirit and scope of the invention. As analternative, the permanganate can be introduced as an aerosol into thegas phase using a microporous diffuser along with air-ozone duringperoxide treatment. The permanganate might be partially filtered by themicroporous screen wall, so this might be a less effective approach.

Accordingly, other embodiments are within the scope of the followingclaims.

1. A method of in situ treating of groundwater, the method comprises:introducing an air stream including ozone gas delivered to thegroundwater with a manganate or a permanganate to decompose contaminantspresent in the groundwater, wherein the manganate or permanganate ispresent in a quantity up to 40 percent liquid volume as a liquid thatcoats the air stream including ozone gas.
 2. The method of claim 1wherein the permanganate is delivered as a coating over microbubblesincluding the air/ozone gas stream.
 3. The method of claim 1 wherein themanganate is delivered as a coating over microbubbles including air andozone gas.
 4. The method of claim 1 wherein introducing includesintroducing air and ozone as gas and the permanganate as a liquid into alaminar microporous diffuser.
 5. The method of claim 1 wherein themanganate is a permanganate precursor and is delivered as a coating overmicrobubbles including the air/ozone gas stream.
 6. The method of claim4 wherein the microporous diffuser has a pore size in the range of about0.1 to 200 microns.
 7. The method of claim 2 wherein the air/ozone hasup to 10% ozone by volume as a gas entrapped in microbubbles.
 8. Themethod of claim 1 wherein introducing includes introducing air and ozoneas a gas mixture entrapped in microbubbles and sodium permanganate as aliquid coating over the microbubbles.
 9. The method of claim 8 whereinthe air/ozone has up to 10% ozone by volume, as a gas entrapped inmicrobubbles.
 10. The method of claim 8 wherein air/ozone with ozone upto 10% volume as a gas entrapped in microbubbles and potassiumpermanganate as a liquid coating over the microbubbles.
 11. The methodof claim 1 wherein the manganate is potassium manganate.
 12. A method oftreating contaminants in a formation, the method comprises: introducinga hydro-peroxide into the formation; and introducing an air/ozone gasstream delivered with a permanganate or a manganate into the formationto decompose the contaminants, wherein the permanganate or the manganateforms a coating over microbubbles of the air and ozone gas mixture,wherein the manganate or permanganate is present in a quantity up to 40percent liquid volume as a liquid that coats the microbubbles.
 13. Themethod of claim 12 wherein the hydro-peroxide is delivered as a surfacelayer over microbubbles including an air/ozone gas stream.
 14. Themethod of claim 12 wherein the manganate is delivered as a surface layerover microbubbles including the air/ozone gas stream, and thehydro-peroxide is delivered as a surface layer over differentmicrobubbles including an air/ozone gas stream.
 15. The method of claim12 wherein introducing peroxide includes introducing air and ozone as agas and the hydro-peroxide as a liquid into a microporous diffuser. 16.The method of claim 12 wherein introducing permanganate includesintroducing air and ozone as a gas and the permanganate as a liquid intoa microporous diffuser.
 17. The method of claim 12 further comprises:waiting for a period of time after introducing the hydro-peroxide beforeintroducing the permanganate or the manganate.
 18. The method of claim12 further comprises: waiting for a period of time after introducing thehydro-peroxide before introducing the permanganate or the manganate toallow the hydro-peroxide to decompose before introducing thepermanganate or the manganate.
 19. The method of claim 12 whereinintroducing of the hydro-peroxide uses a first microporous diffuser andthe air-ozone gas stream with a permanganate or a manganate uses asecond microporous diffuser with the first and second microporousdiffusers having a pore size in the range of about 0.1 to 200 microns.20. The method of claim 18 wherein the permanganate is sodiumpermanganate, and introducing includes introducing air and ozone as agas entrapped in microbubbles and sodium permanganate as a liquidcoating over the microbubbles.
 21. The method of claim 18 wherein thepermanganate is sodium permanganate and air/ozone is ozone up to 10%volume as a gas entrapped in microbubbles and potassium permanganate isin a ratio of 1-20 to 1 of permanganate to ozone.
 22. A method of insitu treating of groundwater comprises: providing a source of manganate;introducing the manganate and air/ozone gas through a diffuser into asoil formation with the manganate delivered as a coating overmicrobubbles including the air/ozone gas stream, wherein the manganateis present in a quantity up to 40 percent liquid volume as a liquid thatcoats the microbubbles.
 23. The method of claim 22 wherein the manganateis potassium manganate.
 24. The method of claim 1 wherein the relativeconcentrations of manganate or permanganate to ozone are in a molarratio of 1-20 to 1.